The extent of non-Born-Oppenheimer coupling in the reaction of Cl(2P) with para-H2.
Elementary triatomic reactions offer a compelling test of our understanding of the extent of electron-nuclear coupling in chemical reactions, which is neglected in the widely applied Born-Oppenheimer (BO) approximation. The BO approximation predicts that in reactions between chlorine (Cl) atoms and molecular hydrogen, the excited spin-orbit state (Cl*) should not participate to a notable extent. We report molecular beam experiments, based on hydrogen-atom Rydberg tagging detection, that reveal only a minor role of Cl*. These results are in excellent agreement with fully quantum-reactive scattering calculations based on two sets of ab initio potential energy surfaces. This study resolves a previous disagreement between theory and experiment and confirms our ability to simulate accurately chemical reactions on multiple potential energy surfaces.
Wang
Xingan
X
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, People's Republic of China.
Dong
Wenrui
W
Xiao
Chunlei
C
Che
Li
L
Ren
Zefeng
Z
Dai
Dongxu
D
Wang
Xiuyan
X
Casavecchia
Piergiorgio
P
Yang
Xueming
X
Jiang
Bin
B
Xie
Daiqian
D
Sun
Zhigang
Z
Lee
Soo-Y
SY
Zhang
Dong H
DH
Werner
Hans-Joachim
HJ
Alexander
Millard H
MH